2,2'-Bi[benzo[b]thiophene]: An unexpected isolation of the benzo[b]thiophene dimer

Article abstract of DOI:10.1107/S2053229614009401

The crystal structure of 2,2'-bi[benzo[b]thiophene], C₁₆H ₁₀S₂, at 173K has triclinic (P1) symmetry. It is of interest with respect to its apparent mode of synthesis, as it is a by-product of a Stille cross-coupling reaction in which it was not explictly detected by spectroscopic methods. It was upon crystal structure analysis of a specimen isolated from the mother liquor that this reaction was determined to give rise to the title compound, which is a dimer arising from the starting material. Two independent half-molecules of this dimer comprise the asymmetric unit, and the full molecules are generated via inversion centers. Both molecules in the unit cell exhibit ring disorder, and they are essentially identical because of their rigidity and planarity.

Full text of DOI:10.1107/S2053229614009401

research papers
Acta Crystallographica Section C
catalyst-reduction step of the cross-coupling. Reductive
elimination would then give rise to the observed dimer.
Although only a minor impurity in the isolated desired
product, by-product (I) was the sole species identified during
single-crystal structure determination. Whilst impurities from
cross-coupling reactions can occur, this study demonstrates
the importance of reconciling the crystal structures from cross-
coupling reactions with the identity of the material in the bulk
product.
Structural Chemistry
ISSN 2053-2296
0
2
,2 -Bi[benzo[b]thiophene]: an
unexpected isolation of the
benzo[b]thiophene dimer
a
b
Eugene Y. Cheung, * Lewis D. Pennington, Michael D.
b
c
Bartberger and Richard J. Staples
a
b
Amgen Inc., 360 Binney Street, Cambridge, MA 02142, USA, Amgen Inc., One
c
Amgen Center Drive, Thousand Oaks, CA 91320, USA, and Department of
Chemistry and Chemical Biology, Chemistry Building, Michigan State University,
East Lansing, MI 48824, USA
Correspondence e-mail: eugene.cheung@amgen.com
Received 8 April 2014
Accepted 26 April 2014
2
. Experimental
0
2.1. Synthesis and crystallization
The crystal structure of 2,2 -bi[benzo[b]thiophene], C H S ,
10 2
16
at 173 K has triclinic (P1) symmetry. It is of interest with
respect to its apparent mode of synthesis, as it is a by-product
of a Stille cross-coupling reaction in which it was not explictly
detected by spectroscopic methods. It was upon crystal
structure analysis of a specimen isolated from the mother
liquor that this reaction was determined to give rise to the title
compound, which is a dimer arising from the starting material.
Two independent half-molecules of this dimer comprise the
asymmetric unit, and the full molecules are generated via
inversion centers. Both molecules in the unit cell exhibit ring
disorder, and they are essentially identical because of their
rigidity and planarity.
Compound (I) was synthesized using a one-step procedure
starting from (benzo[b]thiophen-2-yl)tributylstannane (3.0 g,
7
(
4
.1 mmol) and dichloridobis(triphenylphosphane)palladium(II)
0.33 g, 0.47 mmol). 2-Chloro-3-methylpyridine (0.60 g,
.7 mmol), while present in the reaction mixture (9.4 ml
tetrahydrofuran, reflux, 43 h), did not participate in the di-
merization reaction.
After completion of the cross-coupling reaction, as deter-
mined by high-performance liquid chromatography–mass
spectroscopy (HPLC–MS), the reaction mixture was adsorbed
onto silica gel and subjected to flash chromatography (19:1
hexane–ethyl acetate). The isolated material was re-subjected
to silica-gel flash chromatography (19:1 hexane–ethyl acetate)
Keywords: crystal structures; chemical reactions and
mechanisms; computational chemistry; pharmaceutical
compounds; structure and spectroscopy; by-products.
to remove residual undesired by-products (e.g. Bu SnX resi-
3
dues). A portion of the purified material (48 mg of 1.0 g, 94%
1
yield, >95% purity by HPLC–MS and H NMR) was dissolved
in diisopropyl ether (1.0 ml) and the resulting solution was
filtered through a 0.45 mm Teflon filter into an uncapped small
vial, which was then placed into a large vial containing hexane
(4.0 ml). Vapor diffusion led to the crystallization of a cluster
of solid, of which one crystal appeared to be suitable for
single-crystal X-ray diffraction analysis. Although the solid
was colorless, the selected crystal was clearer than its
surroundings.
1
. Introduction
This account of the structural chemistry of 2,2 -bi[benzo-
b]thiophene], (I), is of a rather serendipitous nature. The
0
[
original intent was to utilize (benzo[b]thiophen-2-yl)tributyl-
stannane in a Stille cross-coupling reaction (Espinet &
Echavarren, 2004) with 2-chloro-3-methylpyridine to yield
1
2-(benzo[b]thiophen-2-yl)-3-methylpyridine. Surprisingly, analy-
With regard to the H NMR spectroscopic data, a very small
sis of the crystals that were grown and harvested after the
reaction did not support the structure of the desired
compound, but rather that of (I), which is a by-product formed
during the cross-coupling reaction. The generalized cross-
aberrant singlet was noted in the aromatic region, and if this
tiny peak is assumed to be that of a single proton of compound
(I), then (I) was present at less than 3 mol% in solution,
perhaps even as low as 2 mol%. The elusiveness of (I) in
solution is further established by its total lack of appearance in
the HPLC–MS data. However, once the unexpected X-ray
crystal structure was obtained, re-evaluation of the bulk
material in a deliberate search for this by-product by thin-
layer chromatography (TLC) revealed traces of it.
2
coupling reaction involves a halogenated sp -hybridized
2
0
species R reacting with an sp -hybridized species R that is
bonded to a sterically hindered metal core. In order for
homodimer (I) to form, the species benzo[b]thiophene–Pd–
II
0
benzo[b]thiophene must have formed during the Pd to Pd
Acta Cryst. (2014). C70, 547–549
doi:10.1107/S2053229614009401
# 2014 International Union of Crystallography 547

research papers
Table 1
Experimental details.
Crystal data
Chemical formula
16 10 2
C H S
M
r
266.36
Triclinic, P1
173
5.8415 (1), 7.6197 (1), 14.2782 (2)
76.286 (1), 81.118 (1), 88.699 (1)
609.94 (2)
Crystal system, space group
Temperature (K)
a, b, c (A)
˚
ꢀ
ꢁ
, ꢂ, ꢃ ( )
˚
3
V (A )
Z
Radiation type
ꢄ (mm )
Crystal size (mm)
2
Cu Kꢁ
3.73
0.36 ꢃ 0.32 ꢃ 0.04
ꢂ1
Data collection
Diffractometer
Bruker APEXII CCD area-detector
diffractometer
Multi-scan (SADABS; Sheldrick,
Absorption correction
1
996)
Figure 1
T
min, Tmax
0.348, 0.853
8960, 2313, 2129
The asymmetric unit of (I), showing the two molecules in the unit cell.
S1AA and S1BA are generated by the inversion center. Displacement
ellipsoids are drawn at the 50% probability level.
No. of measured, independent and
observed [I > 2ꢅ(I)] reflections
R
int
0.036
0.618
˚
ꢂ1
)
(sin ꢆ/ꢇ)max (A
Refinement
2
2
2
R[F > 2ꢅ(F )], wR(F ), S
No. of reflections
No. of parameters
0.036, 0.112, 0.93
2313
177
H-atom parameters constrained
generation of the rest of the molecule by symmetry. The C—C
bond distances between the two halves of each molecule
˚
across the inversion center are 1.448 (3) and 1.447 (3) A,
H-atom treatment
˚
ꢂ3
)
Áꢈmax, Áꢈmin (e A
0.29, ꢂ0.23
suggestive of the fact that this C—C bond has double-bond or
aromatic character, a conclusion which is reinforced by the
planarity of the molecules.
Computer programs: COSMO (Bruker, 2009), APEX2 (Bruker, 2010), SAINT (Bruker,
010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and SHELXTL
2
(Sheldrick, 2008).
During the course of the refinement, it became clear that
there was disorder of the benzo[b]thiophene ring. The S atom
was found to be disordered with the C atom at the 7-position,
1
The H NMR spectra are available in the Supporting
1
ꢀ
information. The ‘aberrant singlet’ is at ꢀ 7.51 in the H NMR
expansion and integrates to 0.02 (2 mol% if it is one proton).
H NMR (400 MHz, chloroform-d): ꢀ 8.54 (d, J = 4.3 Hz, 1H),
.92–7.85 (m, 1H), 7.84–7.78 (m, 1H), 7.69 (s, 1H), 7.58 (d, J =
.6 Hz, 1H), 7.41–7.31 (m, 2H), 7.16 (dd, J = 4.7, 7.6 Hz, 1H),
.67 (s, 3H).
meaning that the entire molecule is flipped 180 over its long
axis. The center of inversion makes it impossible for the
disorder to arise from the presence of molecules with the syn
geometry because the inversion center necessitates that a half-
molecule of (I) generates the other half of the molecule with
the opposing conformation. As there are two independent
half-molecules of (I) in the asymmetric unit, if we designate
one molecule as A and the other as B, molecule A is 61% in its
major orientation and 39% in its minor, whereas molecule B is
1
7
7
2
2
.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. C-bound H atoms were
placed in calculated positions and constrained as riding atoms,
72% in its major orientation and 28% in its minor.
˚
with C—H = 0.95 A and U (H) = 1.2U (C).
iso
eq
The additional atoms arising from the disorder of (I) (see x3
for more details) were located in Fourier difference maps. The
disorder was modeled by refining the occupancies of the C and
S atoms involved in the disorder. The geometries from the
refinement were found to be reasonable without the applica-
tion of restraints, but the atomic displacement parameters of
the two positions for each disordered atom were constrained
to be equal.
Initial assessment of the crystal structure of (I) suggested
that there were two independent benzo[b]thiophene rings in
the asymmetric unit. This would have been suggestive of their
having become disengaged from the stannane starting mate-
rial during the course of the reaction. However, their proxi-
mity to an inversion center imposes a symmetry equivalent
3
. Results and discussion
˚
that is 1.448 A from the C atom at the 8-position, which could
only be explained if dimerization had occurred (Fig. 1). The
The crystal structure of (I) obtained from the present structure
determination was found to contain two independent half-
molecules of (I) in the asymmetric unit (Fig. 1). The proximity
of each half-molecule to an inversion center results in the
0
C—C bond length is similar to that observed for 2,2 -bithio-
˚
phene, which was reported to be 1.448 A (Ali-Adib et al.,
1984).
ꢁ
5
48 Cheung et al.
C
16
H S
10 2
Acta Cryst. (2014). C70, 547–549

research papers
ꢀ
ꢀ
torsion angle of 157 . A local minimum exists at 44 , which
represents an offset syn conformation. A fully planar syn
ꢀ
conformation at an S—C—C—S torsion angle of 0 is calcu-
lated to be an energy maximum. Neither syn conformation is
observed in the present crystal structure.
The molecular packing arrangement of (I) shows that the
molecules do not have strong intermolecular contacts with
each other (Fig. 2). The centroid-to-centroid distance between
˚
the closest neighboring benzene rings of (I) is 4.72 A, and
noncovalent interactions such as ꢉ–ꢉ are not present in this
crystal structure, although possible C—Hꢄ ꢄ ꢄꢉ contacts may be
identified (e.g. C5B—H5BA and C5A—H5AA to neighboring
intermolecular ꢉ-systems). Without stronger interactions to
lock the orientations of the molecules in the solid state, the
existence of disorder for this planar and symmetric molecule
seems sensible.
In conclusion, while the cross-coupling reaction of (benzo-
b]thiophen-2-yl)tributylstannane and 2-chloro-3-methylpyri-
[
dine using dichloridobis(triphenylphosphane)palladium(II) as
the pre-catalyst resulted in almost exclusively the desired
compound as analyzed by spectroscopic methods (>95%),
dimer (I) formed in sufficient amounts to crystallize and
become the dominant species in the specimen as analyzed by
single-crystal X-ray diffraction. Because the prospect of
dimerization is general to cross-coupling reactions, the results
of single-crystal analysis of a specimen arising from such a
reaction mixture should be carefully compared with spectro-
scopic data in order to determine how representative the
crystal structure is of the surrounding solid product.
Figure 2
A packing diagram for (I), viewed along the c axis. H atoms have been
omitted for clarity. Only one configuration of the disordered molecules is
shown.
Owing to the planarity of each half-molecule and their
relationship with the inversion center, the conformations of
both independent molecules of (I) are essentially identical.
The five- and six-membered rings are both planar, which was
also reported for the crystal structure of the monomer
benzo[b]thiophene (Pelletier & Brisse, 1994; Chaloner et al.,
The authors thank Christopher N. Wilde for collecting the
NMR spectra.
Supporting information for this paper is available from the IUCr
electronic archives (Reference: UK3096).
1994). In (I), the S—C—C—S torsion angle that separates the
two halves of each molecule is 180 (as depicted in Scheme 2).
References
ꢀ
Ali-Adib, Z., Rawas, A. & Sutherland, H. H. (1984). Acta Cryst. A40, C277.
Bruker (2009). COSMO. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
ꢀ
A 0 torsion angle occurs when the S atoms are syn to one
ꢀ
another and a 180 torsion angle occurs when they are anti to
each other.
Chaloner, P. A., Gunatunga, S. R. & Hitchcock, P. B. (1994). Acta Cryst. C50,
The geometric results of this crystal structure determination
complement the computational study performed by Hayashi
1941–1942.
Espinet, P. & Echavarren, A. M. (2004). Angew. Chem. Int. Ed. 43, 4704–4734.
Hayashi, N. & Higuchi, H. (2009). Heterocycles, 74, 763–769.
Pelletier, M. & Brisse, F. (1994). Acta Cryst. C50, 1942–1945.
Sheldrick, G. M. (1996). SADABS. University of G o¨ ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
& Higuchi (2009). In their work, the calculations predicted
that (I) would have two minima in its energy landscape. The
global minimum is the anti conformation at an S—C—C—S
ꢁ
Acta Cryst. (2014). C70, 547–549
Cheung et al.
C
16
H S
10 2
549

supplementary materials
supplementary materials
Acta Cryst. (2014). C70, 547-549 [doi:10.1107/S2053229614009401]
2
,2′-Bi[benzo[b]thiophene]: an unexpected isolation of the benzo[b]thiophene
dimer
Eugene Y. Cheung, Lewis D. Pennington, Michael D. Bartberger and Richard J. Staples
Computing details
Data collection: COSMO (Bruker, 2009); cell refinement: APEX2 (Bruker, 2010); data reduction: SAINT (Bruker, 2010);
program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97
(Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication:
SHELXTL (Sheldrick, 2008).
2,2′-Bi[benzo[b]thiophene]
Crystal data
C
16 10
H S
2
Z = 2
M
r
= 266.36
F(000) = 276
D = 1.450 Mg m
x
−3
Triclinic, P1
Hall symbol: -P 1
a = 5.8415 (1) Å
b = 7.6197 (1) Å
c = 14.2782 (2) Å
α = 76.286 (1)°
β = 81.118 (1)°
γ = 88.699 (1)°
Cu Kα radiation, λ = 1.54178 Å
Cell parameters from 5762 reflections
θ = 3.2–72.2°
µ = 3.73 mm
T = 173 K
−1
Plate, colourless
0.36 × 0.32 × 0.04 mm
3
V = 609.94 (2) Å
Data collection
Bruker APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
Detector resolution: 836.6 pixels mm
ω and/f 0.5° scans
Absorption correction: multi-scan
8960 measured reflections
2313 independent reflections
2129 reflections with I > 2σ(I)
R
int = 0.036
-1
θmax = 72.2°, θmin = 3.2°
h = −5→7
k = −9→9
l = −16→17
(
SADABS; Sheldrick, 1996)
T
min = 0.348, Tmax = 0.853
Refinement
2
Refinement on F
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Least-squares matrix: full
R[F > 2σ(F )] = 0.036
2
2
2
wR(F ) = 0.112
S = 0.93
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
2
1
0
313 reflections
77 parameters
restraints
Acta Cryst. (2014). C70, 547-549
sup-1

supplementary materials
2
2
2
−3
w = 1/[σ (F
where P = (F
Δ/σ)max < 0.001
o
) + (0.070P) + 0.3344P]
Δρmax = 0.29 e Å
2
2
−3
o
+ 2F
c
)/3
Δρmin = −0.23 e Å
(
Special details
Experimental. Data were collected using a Bruker CCD (charge-coupled device)-based diffractometer equipped with an
Oxford low-temperature apparatus operating at 173 K. A suitable crystal was chosen and mounted on a nylon loop using
mineral oil for copper radiation. Data were measured using ω and φ scans of 1.0° per frame for 30 s. The total number of
images was based on results from the program COSMO, where redundancy was expected to be 4 and completeness to
0.83 to 100%. Cell parameters were retrieved using APEX2 software and refined using SAINT on all observed reflections.
Data reduction was performed using the SAINT software, which corrects for Lp and decay. Scaling and absorption
corrections were performed by the SADABS program. The structures were solved by the direct method using the
SHELX90 program and refined by the least-squares method on F2 using SHELXL93, incorporated in SHELXTL version
6.1.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
2
2
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,
2
2
2
conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > σ(F ) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F
2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
The following atoms were constrained to having the same thermal values. eadp c7b c7bb eadp s1b s1bb eadp c7a c7ab
eadp s1a s1ab
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Occ. (<1)
S1A
−0.21435 (15)
0.1790 (7)
0.3134
0.36901 (11)
0.5360 (5)
0.5998
0.63774 (6)
0.5940 (3)
0.5566
0.0264 (2)
0.0281 (8)
0.034*
0.6131 (12)
0.6131 (12)
0.6131 (12)
0.3869 (12)
0.3869 (12)
0.3869 (12)
C7A
H7AB
S1AB
C7AB
H7AA
C1A
0.2585 (3)
−0.1321 (10)
−0.2717
0.5707 (2)
0.4023 (8)
0.3466
0.58009 (12)
0.6306 (5)
0.6251
0.0264 (2)
0.0281 (8)
0.034*
−0.0686 (3)
−0.1582 (3)
−0.3037
0.3982 (2)
0.3364 (2)
0.2750
0.72842 (13)
0.82716 (14)
0.8465
0.0297 (4)
0.0354 (4)
0.042*
C2A
H2AA
C3A
−0.0319 (3)
−0.0921
0.3661 (3)
0.3259
0.89592 (14)
0.9633
0.0387 (4)
0.046*
H3AA
C4A
0.1830 (3)
0.2681
0.4543 (2)
0.4722
0.86815 (14)
0.9168
0.0375 (4)
0.045*
H4AA
C5A
0.2734 (3)
0.4201
0.5157 (2)
0.5755
0.77119 (14)
0.7528
0.0339 (4)
0.041*
H5AA
C6A
0.1472 (3)
0.0106 (3)
0.24675 (11)
0.6423 (7)
0.7830
0.4891 (2)
0.4855 (2)
0.11677 (9)
−0.0348 (4)
−0.0949
0.70008 (13)
0.55109 (12)
0.40529 (5)
0.3769 (2)
0.3886
0.0287 (4)
0.0238 (3)
0.0273 (2)
0.0284 (7)
0.034*
C8A
S1B
0.7234 (16)
0.7234 (16)
0.7234 (16)
0.2766 (16)
0.2766 (16)
0.2766 (16)
C7B
H7BA
S1BB
C7BB
H7BB
C1B
0.7176 (4)
0.3217 (14)
0.1844
−0.0595 (3)
0.0846 (11)
0.1269
0.37345 (17)
0.3997 (7)
0.4319
0.0273 (2)
0.0284 (7)
0.034*
0.3556 (3)
0.0977 (2)
0.29021 (13)
0.0277 (4)
Acta Cryst. (2014). C70, 547-549
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supplementary materials
C2B
0.2467 (3)
0.0999
0.1641 (2)
0.2199
0.20905 (15)
0.2155
0.0374 (4)
0.045*
H2BA
C3B
0.3569 (4)
0.2853
0.1470 (3)
0.1926
0.11913 (15)
0.0630
0.0449 (5)
0.054*
H3BA
C4B
0.5712 (4)
0.6437
0.0642 (3)
0.0542
0.10913 (14)
0.0463
0.0437 (5)
0.052*
H4BA
C5B
0.6794 (3)
0.8248
−0.0034 (2)
−0.0611
0.18894 (14)
0.1817
0.0362 (4)
0.043*
H5BA
C6B
0.5729 (3)
0.4907 (3)
0.0141 (2)
0.0120 (2)
0.28060 (13)
0.44888 (12)
0.0276 (4)
0.0244 (3)
C8B
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
S1A
0.0193 (4)
0.0174 (16)
0.0193 (4)
0.0174 (16)
0.0265 (8)
0.0266 (8)
0.0438 (10)
0.0432 (10)
0.0264 (8)
0.0271 (8)
0.0186 (7)
0.0215 (4)
0.0210 (14)
0.0215 (4)
0.0210 (14)
0.0246 (8)
0.0327 (9)
0.0622 (13)
0.0542 (12)
0.0305 (9)
0.0246 (8)
0.0202 (7)
0.0274 (4)
0.0246 (16)
0.0274 (4)
0.0246 (16)
0.0232 (8)
0.0290 (9)
0.0350 (9)
0.0345 (9)
0.0264 (8)
0.0205 (7)
0.0174 (7)
0.0283 (4)
0.0254 (14)
0.0283 (4)
0.0254 (14)
0.0210 (7)
0.0272 (9)
0.0337 (10)
0.0448 (11)
0.0346 (9)
0.0211 (7)
0.0202 (7)
0.0304 (4)
0.0399 (17)
0.0304 (4)
0.0399 (17)
0.0403 (10)
0.0450 (10)
0.0327 (9)
0.0402 (10)
0.0490 (11)
0.0354 (9)
0.0339 (9)
0.0325 (3)
0.0402 (15)
0.0325 (3)
0.0402 (15)
0.0374 (9)
0.0544 (12)
0.0405 (11)
0.0319 (9)
0.0453 (11)
0.0375 (9)
0.0331 (9)
−0.0038 (3)
−0.0013 (3)
0.0000 (15)
−0.0013 (3)
0.0000 (15)
−0.0077 (7)
0.0030 (7)
−0.0039 (3)
−0.0056 (12)
−0.0039 (3)
−0.0056 (12)
−0.0084 (7)
−0.0033 (8)
−0.0046 (8)
−0.0144 (8)
−0.0094 (8)
−0.0043 (7)
−0.0047 (6)
−0.0078 (2)
−0.0096 (10)
−0.0078 (2)
−0.0096 (10)
−0.0075 (6)
−0.0072 (8)
0.0000 (8)
C7A
S1AB
C7AB
C1A
C2A
C3A
C4A
C5A
C6A
C8A
S1B
−0.0006 (13)
−0.0038 (3)
−0.0006 (13)
0.0048 (7)
0.0008 (7)
0.0082 (8)
0.0085 (8)
0.0006 (7)
0.0049 (6)
0.0020 (6)
0.0069 (2)
0.0067 (12)
0.0069 (2)
0.0067 (12)
−0.0013 (6)
0.0045 (7)
−0.0074 (9)
−0.0169 (10)
−0.0035 (7)
−0.0016 (6)
0.0004 (6)
0.0019 (8)
−0.0150 (8)
−0.0054 (7)
0.0003 (7)
−0.0012 (6)
−0.0049 (3)
−0.0076 (13)
−0.0049 (3)
−0.0076 (13)
−0.0034 (7)
−0.0181 (8)
−0.0253 (10)
0.0018 (8)
C7B
S1BB
C7BB
C1B
C2B
C3B
C4B
C5B
C6B
C8B
−0.0125 (8)
−0.0176 (8)
−0.0066 (7)
−0.0065 (6)
0.0017 (7)
−0.0063 (7)
−0.0046 (6)
Geometric parameters (Å, º)
S1A—C1A
1.7136 (19)
S1B—C1B
1.7064 (18)
S1A—C8A
1.7536 (18)
1.344 (4)
1.454 (4)
0.9500
S1B—C8B
1.7442 (17)
1.359 (4)
1.455 (4)
0.9500
C7A—C8A
C7A—C6A
C7A—H7AB
S1AB—C6A
S1AB—C8A
C7AB—C8A
C7AB—C1A
C7AB—H7AA
C1A—C2A
C7B—C8B
C7B—C6B
C7B—H7BA
S1BB—C6B
S1BB—C8B
C7BB—C8B
C7BB—C1B
C7BB—H7BB
C1B—C2B
1.707 (2)
1.745 (2)
1.332 (6)
1.493 (7)
0.9500
1.661 (3)
1.737 (3)
1.334 (9)
1.525 (9)
0.9500
1.397 (3)
1.392 (3)
Acta Cryst. (2014). C70, 547-549
sup-3

supplementary materials
C1A—C6A
C2A—C3A
C2A—H2AA
C3A—C4A
C3A—H3AA
C4A—C5A
C4A—H4AA
C5A—C6A
C5A—H5AA
1.408 (2)
1.377 (3)
0.9500
C1B—C6B
C2B—C3B
C2B—H2BA
C3B—C4B
C3B—H3BA
C4B—C5B
C4B—H4BA
C5B—C6B
C5B—H5BA
1.410 (2)
1.378 (3)
0.9500
1.394 (3)
0.9500
1.392 (3)
0.9500
1.376 (3)
0.9500
1.376 (3)
0.9500
1.397 (3)
0.9500
1.395 (3)
0.9500
i
ii
C8A—C8A
1.447 (3)
C8B—C8B
1.448 (3)
C1A—S1A—C8A
C8A—C7A—C6A
C8A—C7A—H7AB
C6A—C7A—H7AB
C6A—S1AB—C8A
C8A—C7AB—C1A
C8A—C7AB—H7AA
C1A—C7AB—H7AA
C2A—C1A—C6A
C2A—C1A—C7AB
C6A—C1A—C7AB
C2A—C1A—S1A
C6A—C1A—S1A
C7AB—C1A—S1A
C3A—C2A—C1A
C3A—C2A—H2AA
C1A—C2A—H2AA
C2A—C3A—C4A
C2A—C3A—H3AA
C4A—C3A—H3AA
C5A—C4A—C3A
C5A—C4A—H4AA
C3A—C4A—H4AA
C4A—C5A—C6A
C4A—C5A—H5AA
C6A—C5A—H5AA
C5A—C6A—C1A
C5A—C6A—C7A
C1A—C6A—C7A
C5A—C6A—S1AB
C1A—C6A—S1AB
C7A—C6A—S1AB
C7AB—C8A—C7A
89.14 (9)
117.3 (3)
121.3
C1B—S1B—C8B
C8B—C7B—C6B
90.53 (8)
115.0 (3)
C8B—C7B—H7BA
C6B—C7B—H7BA
C6B—S1BB—C8B
C8B—C7BB—C1B
C8B—C7BB—H7BB
C1B—C7BB—H7BB
C2B—C1B—C6B
C2B—C1B—C7BB
C6B—C1B—C7BB
C2B—C1B—S1B
C6B—C1B—S1B
C7BB—C1B—S1B
C3B—C2B—C1B
C3B—C2B—H2BA
C1B—C2B—H2BA
C2B—C3B—C4B
C2B—C3B—H3BA
C4B—C3B—H3BA
C5B—C4B—C3B
C5B—C4B—H4BA
C3B—C4B—H4BA
C4B—C5B—C6B
C4B—C5B—H5BA
C6B—C5B—H5BA
C5B—C6B—C1B
C5B—C6B—C7B
C1B—C6B—C7B
C5B—C6B—S1BB
C1B—C6B—S1BB
C7B—C6B—S1BB
C7BB—C8B—C7B
122.5
121.3
122.5
87.65 (10)
118.8 (5)
120.6
88.56 (13)
117.9 (6)
121.0
120.6
121.0
120.37 (17)
139.6 (3)
100.1 (3)
122.15 (14)
117.48 (14)
17.4 (2)
120.70 (17)
140.6 (3)
98.7 (3)
123.93 (14)
115.33 (14)
16.7 (3)
118.86 (17)
120.6
118.48 (18)
120.8
120.6
120.8
120.93 (18)
119.5
121.13 (18)
119.4
119.5
119.4
120.82 (18)
119.6
120.90 (19)
119.6
119.6
119.6
119.29 (17)
120.4
119.10 (18)
120.5
120.4
120.4
119.72 (17)
135.6 (2)
104.7 (2)
118.74 (14)
121.54 (15)
16.86 (16)
99.2 (3)
119.68 (17)
132.9 (2)
107.4 (2)
117.14 (16)
123.13 (16)
15.81 (15)
101.0 (4)
129.9 (4)
129.1 (2)
111.6 (4)
10.69 (17)
118.41 (17)
i
ii
C7AB—C8A—C8A
130.4 (3)
130.4 (2)
111.9 (3)
12.79 (19)
117.62 (16)
C7BB—C8B—C8B
i
ii
C7A—C8A—C8A
C7B—C8B—C8B
C7AB—C8A—S1AB
C7A—C8A—S1AB
C7BB—C8B—S1BB
C7B—C8B—S1BB
i
ii
C8A —C8A—S1AB
C8B —C8B—S1BB
Acta Cryst. (2014). C70, 547-549
sup-4

supplementary materials
C7AB—C8A—S1A
C7A—C8A—S1A
12.2 (3)
C7BB—C8B—S1B
C7B—C8B—S1B
10.9 (4)
111.4 (2)
111.80 (18)
119.13 (16)
122.44 (12)
i
ii
C8A —C8A—S1A
118.19 (16)
124.18 (11)
C8B —C8B—S1B
S1AB—C8A—S1A
S1BB—C8B—S1B
C8A—C7AB—C1A—C2A
C8A—C7AB—C1A—C6A
C8A—C7AB—C1A—S1A
C8A—S1A—C1A—C2A
C8A—S1A—C1A—C6A
C8A—S1A—C1A—C7AB
C6A—C1A—C2A—C3A
C7AB—C1A—C2A—C3A
S1A—C1A—C2A—C3A
C1A—C2A—C3A—C4A
C2A—C3A—C4A—C5A
C3A—C4A—C5A—C6A
C4A—C5A—C6A—C1A
C4A—C5A—C6A—C7A
C4A—C5A—C6A—S1AB
C2A—C1A—C6A—C5A
C7AB—C1A—C6A—C5A
S1A—C1A—C6A—C5A
C2A—C1A—C6A—C7A
C7AB—C1A—C6A—C7A
S1A—C1A—C6A—C7A
C2A—C1A—C6A—S1AB
C7AB—C1A—C6A—S1AB
S1A—C1A—C6A—S1AB
C8A—C7A—C6A—C5A
C8A—C7A—C6A—C1A
C8A—C7A—C6A—S1AB
C8A—S1AB—C6A—C5A
C8A—S1AB—C6A—C1A
C8A—S1AB—C6A—C7A
C1A—C7AB—C8A—C7A
177.7 (2)
−1.8 (5)
C8B—C7BB—C1B—C2B
C8B—C7BB—C1B—C6B
C8B—C7BB—C1B—S1B
C8B—S1B—C1B—C2B
C8B—S1B—C1B—C6B
C8B—S1B—C1B—C7BB
C6B—C1B—C2B—C3B
C7BB—C1B—C2B—C3B
S1B—C1B—C2B—C3B
C1B—C2B—C3B—C4B
C2B—C3B—C4B—C5B
C3B—C4B—C5B—C6B
C4B—C5B—C6B—C1B
C4B—C5B—C6B—C7B
C4B—C5B—C6B—S1BB
C2B—C1B—C6B—C5B
C7BB—C1B—C6B—C5B
S1B—C1B—C6B—C5B
C2B—C1B—C6B—C7B
C7BB—C1B—C6B—C7B
S1B—C1B—C6B—C7B
C2B—C1B—C6B—S1BB
C7BB—C1B—C6B—S1BB
S1B—C1B—C6B—S1BB
C8B—C7B—C6B—C5B
C8B—C7B—C6B—C1B
C8B—C7B—C6B—S1BB
C8B—S1BB—C6B—C5B
C8B—S1BB—C6B—C1B
C8B—S1BB—C6B—C7B
C1B—C7BB—C8B—C7B
−176.4 (3)
2.0 (6)
178.0 (12)
178.43 (15)
−1.08 (14)
−1.3 (8)
−174.9 (17)
−177.67 (16)
0.09 (13)
3.4 (11)
0.0 (3)
−0.3 (3)
−179.4 (4)
−179.48 (14)
−0.7 (3)
177.8 (5)
177.30 (13)
0.5 (3)
0.7 (3)
0.1 (3)
0.1 (3)
−0.8 (3)
−0.8 (3)
1.0 (3)
178.2 (2)
178.48 (14)
0.8 (2)
−177.3 (2)
−176.67 (16)
−0.4 (3)
−179.6 (3)
−179.72 (13)
−178.54 (19)
1.1 (3)
−179.2 (3)
−178.24 (12)
178.28 (18)
−0.5 (4)
1.0 (2)
0.4 (2)
−178.52 (14)
1.1 (3)
177.11 (16)
−1.7 (3)
1.0 (2)
−0.7 (2)
−179.4 (2)
−0.3 (3)
177.48 (18)
−1.0 (3)
179.8 (8)
−179.53 (14)
−0.24 (16)
−0.2 (6)
175.4 (8)
178.44 (14)
0.88 (19)
−3.2 (6)
1.6 (4)
−2.5 (6)
i
ii
C1A—C7AB—C8A—C8A
−177.8 (3)
1.8 (5)
C1B—C7BB—C8B—C8B
177.8 (3)
−1.7 (7)
C1A—C7AB—C8A—S1AB
C1A—C7AB—C8A—S1A
C6A—C7A—C8A—C7AB
C1B—C7BB—C8B—S1BB
C1B—C7BB—C8B—S1B
C6B—C7B—C8B—C7BB
−177.2 (16)
−0.7 (3)
172 (3)
2.1 (4)
i
ii
C6A—C7A—C8A—C8A
178.7 (2)
−179.7 (10)
−0.4 (3)
C6B—C7B—C8B—C8B
−178.2 (2)
−173.6 (11)
1.1 (3)
C6A—C7A—C8A—S1AB
C6A—C7A—C8A—S1A
C6A—S1AB—C8A—C7AB
C6A—S1AB—C8A—C7A
C6B—C7B—C8B—S1BB
C6B—C7B—C8B—S1B
C6B—S1BB—C8B—C7BB
C6B—S1BB—C8B—C7B
−0.9 (3)
0.5 (4)
0.2 (8)
5.1 (9)
i
ii
C6A—S1AB—C8A—C8A
178.82 (17)
−0.61 (13)
2.1 (12)
C6B—S1BB—C8B—C8B
−179.00 (18)
−0.81 (16)
−6 (2)
C6A—S1AB—C8A—S1A
C1A—S1A—C8A—C7AB
C1A—S1A—C8A—C7A
C6B—S1BB—C8B—S1B
C1B—S1B—C8B—C7BB
C1B—S1B—C8B—C7B
0.8 (2)
−0.65 (18)
Acta Cryst. (2014). C70, 547-549
sup-5

supplementary materials
i
ii
C1A—S1A—C8A—C8A
C1A—S1A—C8A—S1AB
−178.41 (17)
1.02 (12)
C1B—S1B—C8B—C8B
178.71 (17)
0.53 (13)
C1B—S1B—C8B—S1BB
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1.
Acta Cryst. (2014). C70, 547-549
sup-6

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